Reaction product of epichlorohydrin compound and beta-alkylamine

ABSTRACT

Reaction product of a epichlorohydrin compound and a betaalkylamine. The latter is defined as an alkylamine in which the alkyl group is attached to the nitrogen atom at its beta carbon atom. The reaction product is particularly useful as an additive to retard deterioration of hydrocarbon oils.

United States atent Rosenwald 1 Aug. 22, 1972 [54] REACTION PRODUCT OF[56] References Cited EPICHLOROHYDRIN CONIPOUND AND BETA ALKYLAMINEUNITED STATES PATENTS 72 Inventor; Robert Rosenwald, western 3,497,5562/1970 Lanner et a1 ..260/584 R Springs, ]11 3,189,652 6/1965 Pollitzer..260/584 R [73] Assignee: gnivlgil'sal 031 Products Company, PrimaryExaminer joseph Rebold es ames Assistant Examiner-Richard L. Raymond[22] Filed: Feb. 24, 1969 Attorney-James R. Hoatson, Jr. and Bernard L.21 App1.No.: 801,853 Kramer Related us. Application Data [57] ABSTRACT[63] Continuation-in-part of Ser. No. 463,901, June Reaction product ofa epichlorohydrin compound and 14, 1965, Pat. No. 3,457,053. abeta-alkylamine. The latter is defined as an alkylamine in which thealkyl group is attached to the --260/584 R 72, 260/583 R, nitrogen atomat its beta carbon atom. The reaction 260/583 P product is particularlyuseful as an additive to retard [51] Int. Cl. ..C07c 91/02, C07c 91/ 10deterioration f hydrocarbon i [58] Field of Search .260/584 R, 585R, 583R 3 Claims, N0 Drawings REACTION PRODUCT OF EPICI-ILOROHYDRIN COMPOUNDAND BETA-ALKYLAMINE CROSS REFERENCE TO RELATES APPLICATIONS DESCRIPTIONOF THE INVENTION The novel compound of the present invention is thereaction product formed by the reaction of a particular type of aminewith an epihalohydrin compound. The particular type of amine for use informing the reaction product is critical and is a beta-alkyl amine,herein referred to as beta-amine, and is one in which the alkyl group isattached to the nitrogen atom at the beta or second carbon atom of thealkyl group. It now has been found that the use of the beta-amine inpreparing the reaction product of the present invention offersunexpected advantages over reaction products prepared when usingalpha-alkyl amines, herein referred to as alpha-amines, in which thealkyl group is attached to the nitrogen atom at the terminal carbon atomof the alkyl group.

Very effective additives for hydrocarbon oils, particularly hydrocarbonoils higher boiling than gasoline, have been prepared by the reaction ofalpha-amines with epihalohydrin compounds. While these additives arevery effective, they do have the disadvantage of high pour point and arehigh cloud point. In other words the reaction product tends to gel andsolidify at ambient temperature, especially during the colder seasons ofthe year. When this occurs, it is objectionable because the user of theadditive either must handle a product which is part liquid and partsolid or the user must go through the added time and expense of heatingthe compound in order to form a liquid product. As can be wellappreciated, this added requirement interferes with the ready use oftheadditive and, in some cases, may mean the difference between adecision to use the additive commercially or not to so use it.

As will be illustrated by the data in the examples appended to thepresent specifications, the reaction product prepared from thebeta-amine is of considerably lower pour point and lower cloud point.Any suitable beta-amine is used as a reactant in preparing the noveladditive of the present invention. In one embodiment the beta-amine is amonoamine and, while it may contain from four to about 50 carbon atoms,it preferably contains from about six to about carbon atoms.Illustrative preferred beta-amines include lmethylpentylamine,l-methylhexylamine, l-methylheptylamine, l-methyloctylamine,l-methylnonylamine, l-methyldecylamine, l-methylundecylamine,l-methyldodecylamine, l-methyltridecylamine, l-methyltetradecylamine,l-methylpentadecylamine, l-methylhexadecylamine,l-methylheptadecylamine, l-methyloctadecylamine,l-rnethylnonadecylamine, etc. It is understood that the long alkyl chainmay be straight chain or may contain branching in the chain other thanany additional carbon attachment to the beta carbon atom.

In another embodiment the beta-amine is a polyarnine containing at leastone beta-amine configuo propylenediamine,

ration. Illustrative preferred beta-diamines include N- 1-methylpentylpropylenediamine, N- 1 -methylhexylpropylenediamine, N- l-methylheptylpropylenediamine, N- l-methyloctylpropylenediamine,N-l-methylnonylpropylenediamine, N- l -methyldecylpropylenediarnine, N-l -methylundecyl-propylenediamine, N- 1 -methyldodecyl-propylenediamine,N-l-methyltridecyl- N- 1 -methyltetradecylpropylenediamine,N-l-methylpentadecylpropylenediamine,N-l-rnethylhexadecylpropylenediamine,N-l-methylheptadecylpropylenediamine, N-l-methyloctadecylpropylenediamine, N-l-methylnonadecylpropylenediamine,etc., similarly substituted ethylenediamines, butylenediamines,pentylenediamines, hexylenediamines, heptylenediarnines, etc., as wellas dialkylenetriamines, trialkylenetetramines, tetralkylenepentamines,etc., containing at least one beta-amine configuration. Here again, itis understood that the long alkyl chain may be straight chain or maycontain branching along the chain other than additional carbon linkageon the beta carbon atom.

While the preferred beta-amines for use in accordance with the presentinvention are beta-alkyl amines, it is understood that the correspondingbeta-alkylene amines may be used but not necessarily with equivalentresults. The beta-alkylene amines, both monoamines and polyamines, willcontain unsaturation in the long alkyl chain. Such beta-amines mayresult when they are prepared from unsaturated fatty acids.

The beta-amines are prepared in any suitable manner. In most methods ofpreparation a mixture of beta-amines may be formed and such mixture ofbetaarnines may be used for reaction with the epihalohydrin compound inaccordance with the present invention.

As hereinbefore set forth the beta-amine is reacted with anepihalohydrin compound. Epichlorohydrin is preferred. Otherepichlorohydrin compounds include 1,2-epoxy-4-chlorobutane,2,3-epoxy-4-chlorobutane, 1,2-epoxy-5-chloropentane,2,3-epoxy-5-chloropentane, etc'. In general the chloro derivatives arepreferred, although it is understood that the corresponding bromo andiodo compounds may be employed. In some cases epidihalohydrin compoundsmay be utilized. It is understood that the different epihalohydrincompounds are not necessarily equivalent and that, as hereinbefore setforth,

epichlorohydrin is preferred.

The beta-amine is reacted with the. epihalohydrin compound in a moleratio of from l to 2 mole proportions of beta-amine to 1 to 1.5 moleproportions of epihalohydrin compound. In a particularly preferredembodiment of the invention, the beta-monoamine is reacted withepichlorohydrin in equal mole proportions, although an excess of one ofthe reactants may be used when desired. A preferred reaction product isa polymeric product prepared by reacting equal mole proportions of theamine and epichlorohydrin and containsfrom about 2 to 20 or morerecurring units and preferably from about 2 to about 10 recurring units.

The desired quantity of beta-amine and epihalohydrin compound may besupplied to the reaction zone and therein reacted, although generally itis preferred to supply one reactant to the reaction zone and thenintroduce the other reactant step-wise. Thus, usually it is preferred tosupply the epichlorohydrin to the reaction zone and to add thebeta-amine stepwise, with stirring. Preferably the reaction ofepichlorohydrin with the second or later portions of beta-amine iseffected at a higher temperature than with the first portion of thebeta-amine. The reaction preferably is effected in the presence of asolvent which may comprise a hydrocarbon and particularly an aromatichydrocarbon including benzene, toluene, xylene, ethylbenzene, cumene,etc., or an alcohol including ethanol, propanol, butanol, etc. Inanother embodiment the solvent may comprise a glycol including ethyleneglycol, propylene glycol, glycerol, etc., or a saturated aliphatichydrocarbon including hexane, heptane, octane, etc.

The reaction of the beta-amine and epihalohydrin is effected at anysuitable temperature which generally will be within the range of fromabout 50 to about 200C. and preferably within the range of from about 60to about 150C. Conveniently, this reaction is effected by heating asolution of epichlorohydrin in aromatic solvent, with stirring,gradually adding the betaamine thereto, and continuing the heating,preferably at a higher temperature until the reaction is completed, orthe reverse order of adding the reactants may be used. In thepreparation of the polymeric reaction product, the reaction mixture,following completion of the reaction of the beta-amine andepihalohydrin, is treated with an inorganic base in order to convert theorganic halide salt of the reaction mixture to an inorganic halide saltand to thereby liberate the free amine for further reaction to form thedesired polymeric product. This may be effected in any suitable mannerand generally is accomplished by reacting the primary reaction productwith a strong inorganic base such as sodium hydroxide, potassiumhydroxide, etc., to form the corresponding metal halide. The reaction toform the metal halide is effected at a temperature within the range offrom about 60 to about 200C. and preferably from about 75 to about 150C.The inorganic base may be added in at least two steps with interveningheating and reacting so that organic halide formed after the firstaddition of inorganic base is in turn reacted to liberate the freeamine.

in one embodiment the product at this stage of manufacture may bewithdrawn from the reaction zone and filtered or otherwise treated toremove the inorganic halide. Generally, however, it is preferred toperform the next step in the same reaction zone without removing theinorganic halide. At the conditions used in forming the polymericreaction product, the inorganic halide is inert and, therefore, itspresence is not objectionable. Regardless of whether or not theinorganic halide is removed, the primary reaction product of the aminecompound and epihalohydrin compound is now further heated and reacted inorder to form the desired linear polymeric reaction product. Thisfurther heating and reacting is at a temperature of from about 75 toabout 200C. and preferably from about 80 to about 15 C.

After formation of the desired polymeric reaction product or before thisstep as mentioned above, the inorganic halide salt is removed in anysuitable manner,

including filtering, centrifugal separation, etc. in some cases, it maybe of advantage to effect the filtration at an elevated temperaturewhich may range from about 35 to about C. or more. When desired, wateror other aqueous solvent may be added to the reaction mixture todissolve and facilitate removal of the inorganic halide salt.

The reaction product prepared in the above manner is a new compositionof matter and accordingly is being so claimed in the presentapplication. The reaction product is recovered as a viscous liquidwhich, as hereinbefore set forth, has a low pour point and low cloudpoint. Generally, it will range from a light through amber color,although, in some cases, it may be of a dark color. For most uses, thereaction product may be dissolved in a suitable solvent, particularly ahydrocarbon and, more particularly, an aromatic hydrocarbon.Accordingly, a convenient method is to allow the reaction product to berecovered in the solvent used during the manufacture thereof and, whennecessary, to add additional solvent to form a final composition of thedesired concentration of active ingredients. However, when desired, thesolvent used during the reaction may be removed by vacuum distillation.

While the reaction product may be used for the stabilization ofgasoline, naphtha, or other relatively low boiling hydrocarbon oils, itis particularly applicable to the stabilization of higher boilinghydrocarbon oils including fuel oil, diesel oil, jet fuel, etc. The fueloils are marketed under various names including burner oil, furnace oiland, of course, various grades of fuel oil. During storage and/or use,these oils undergo deterioration, with the formation of sediment,undesired discoloration, etc. The formation of sediment is objectionablebecause the sediment tends to plug strainers, burner tips, injectors,etc., and, when used as diesel fuel, tends to form varnish and sludge inthe diesel engine. Discoloration of the oil is objectionable for variousreasons, particularly the customers preference for light colored oils.

Deterioration of the jet fuel and burner oil at high temperature also isa serious problem. For example, jet fuel is used as a'heat exchangemedium for hot exhaust gases and deterioration of the jet fuel resultsin plugging of the exchanger coils. This problem of deposit formation inheat exchangers also occurs during the processing of hydrocarbon oils inwhich the hydrocarbon oil charge at a lower temperature is passed intoindirect heat exchange with hot reaction products of the process. Thisserves the economic ad vantage of partially heating the charge to theprocess and of partially cooling the reaction products of the process.Here again, it is important that deposit forma tion be. avoided or atleast reduced to a minimum in order to permit satisfactory andcontinuous operation of the heat exchange system. Otherwise plugging ofthe tubes and/or shell of the heat exchanger will decrease heat transferand eventually will require shutdown of the plant in order to clean theheat exchanger and, if necessary, to replace all or a portion of theheat exchange equipment.

The above difficulties are avoided by incorporating the novel additiveof the present invention into the hydrocarbon oil. The additive servesto retard and/or prevent degradation of the hydrocarbon oil in storageand/or in use, as well as during processing as hereinbefore described.

The additive will be used in hydrocarbon oil in a stabilizingconcentration which will be below about 1 percent by weight and withinthe range of from about 0.0001 percent to about 1 percent and generallyfrom about 0.001 percent to about 0.5 percent by weight. In anotherembodiment the reaction product of the present invention is used inadmixture with certain metal deactivators which appear to increase thepotency of the additive beyond that which normally would be expected andthus, results in a synergistic effect. A particularly preferred metaldeactivator is disalicylaldiarninopropane. Other metal deactivatorsinclude ohydroxybenzalaminophenol, o-hydroxybenzalanthranilic acid,alkylenepolyamine-tetracarboxylic acids and particularlyethylenediaminetetracetic acid, or alkali metal salts thereof. The metaldeactivator is used in a minor amount and, accordingly, in aconcentration of below about 0.5 percent by weight and within the rangeof from about 0.00001 percent to about 0.5 percent and generally fromabout 0.0001 percent to about 0.05 percent by weight.

When desired the additive of the present invention also may be used inconjunction with other antioxidants, cetane improvers, rust inhibitors,etc. Generally, these additives are employed as solutions in suitablesolvents and, when desired, the additive of the present invention may beprepared as a mixture with one or more other additives, preferably as asolution in a suitable solvent, and the same marketed and used as asingle commodity of multiple purpose.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

EXAMPLE I The reaction product of this example was prepared by thereaction of equal mole proportions of a betamonoamine mixture andepichlorohydrin. The mixed beta-monoamines used in this example areavailable commercially as Armeen lJ-7 and comprise a mixture ofbeta-monoarnines containing from aboutseven to about 1 1 carbon atomsper molecule. The mixture of beta-amines has an average molecular weightof 145, an average number of carbon atoms per molecule of 9 and a basicnitrogen equivalent weight of 136 grams.

The reaction was effected by first forming a solution of 93 g. (onemole) of epichlorohydrin in 70 g. of xylene solvent and heating themixture to a pot temperature of 80C. A separate solution of 136 g. ofthe mixed beta-monoamines in 70 g. of xylene solvent was prepared.One-half of the latter solution (0.5 mole of amines) was added to thesolution of epichlorohydrin with stirring and heating to a pottemperature of 8085 C. for about 1 hour, after which time the remainingsolution of beta-monoamine (0.5 mole) was added to the reaction mixture,followed by 60 grams of additional xylene solvent. The reaction mixturewas stirred and heated to a pot temperature of about 110C. for about 4hours. At this time 80 g. of 50 percent sodium hydroxide solution (onemole) was added and the reaction mixture was heated and stirred at a.pot temperature of about 110C. for 3% hours. Following completion of thereaction, 106 g. of water was added and the mixture was allowed tosettle into two phases. Ready separation of phases occurred, the waterphase containing the sodium chloride. The reaction product was shakenwith 8 grams of adsorbent silica gel at 80 C. in order to clear upanyhaze and the mixture'then was filtered and the reaction product wasrecovered as a light yellow clear liquid.

A portion of the reaction product prepared in the above manner wassubjected to vacuum distillation to remove the xylene solvent, and theproduct was recovered as a light yellow clear liquid having an averagemolecular weight of 515 g., a basic nitrogen equivalent weight of 4.61,a tertiary basic nitrogen equivalent weight of 3.0 and an acidity of0.242 meg/g. The reaction product had an average of 2.6 recurring units.

EXAMPLE n The reaction product of this example was prepared insubstantially the same manner as described in Example 1 except that thebeta-monoarnine used in this example was a mixture availablecommercially as Armeen L9 and comprises a mixture of betamonoaminescontaining from about 9 to about 13 carbon atoms per molecule. Thismixture of amines has an average molecular weight of 167 g., an averagenumber of carbon atoms per molecule of 11 and a basic nitrogenequivalent weight of 164 g.

The reaction was effected by first forming a solution of 93 g. (onemole) of epichlorohydrin in 93 g. of xylene solvent and forming aseparate solution of 164 g. (one mole) of the amines in 82 g. of xylenesolvent. As in the preparation of Example 1, the epichlorohydrinsolution was heated and the amine solution was added thereto in twoseparate portions. The reaction vessel was heated initially to a pottemperature of C. for about 1.5 hours and later to a pot temperature upto about 125C. for about 8 hours. Following completion of the reaction,g. of water was added and the mixture was separated in the same manneras described in Example 1, after which the reaction product was shakenwith 4 grams of silica adsorbent and filtered. 'A portion of thereaction product was subjected to vacuum distillation to remove thexylene solvent, to leave the reaction product as a clear amber liquidhaving a total basic nitrogen equivalent weight of 4.24, a tertiarybasic nitrogen equivalent weight of 3.61 and an acidity of 0.196 meq/g.

The reaction product of this example was prepared in substantially thesame manner as described in Example 1, except that the beta-monoamineused in this example was a mixture available commercially as Armeen L-l1 and comprises a mixture of betamonoamines containing from about 1 1 toabout 15 carbon atoms per molecule. This mixture of amines has anaverage molecular weight of 204 g., an average number of carbon atomsper molecule of 13 and a basic nitrogen equivalent weight of 204 g.

A solution of 74.5 g. (0.8 mole) of epichlorohydrin in 75 g. of xylenesolvent was prepared. A separate solution of 162.8 g. (0.8 mole) of theamines in 81 g. of xylene solvent was separately prepared. The

epichlorohydrin solution was heated to a pot temperature of 96C., withstirring, and one-half of the amine solution was-added thereto, withstirring and heating at about 100C. for about 1 hour, after which theremaining portion of the amine solution was added with stirring andheating to a pot temperature of about 133C. for about 6 hours. Then 64g. of 50% sodium hydroxide solution was added with continuous stirringand heating to about 112C. As in the previous preparations water, inthis case 80 grams, was added to the reaction mixture, followed bysettling and separation of layers and then shaking with 8 grams ofsilica adsorbent and filtering to produce a light yellowish clearproduct. A portion of the reaction product was subjected to vacuumdistillation to remove the xylene solvent and to leave a clear yellowishliquid having an average molecular weight of 774 g., a basic nitrogenequivalent weight of 3.87, a tertiary basic nitrogen equivalent weightof 2.59 and an acidity of 0.096 meq/gThe reaction product had an averageof 2.98 recurring units.

EXAMPLE IV The reaction product of this example was prepared insubstantially the same manner as described in the previous examplesexcept that the beta-monoamine used in this example was a mixtureavailable commercially as Armeen L-lS and comprises a mixture ofbeta-monoamines containing from about to about 22 carbon atoms permolecule. This mixture of amines has an average molecular weight of 270g., an average number of carbon atoms per molecule of and a basicnitrogen equivalent weight of 292 grams.

A solution of 56 g. (0.6 mole) of epichlorohydrin in 70 g. of xylenesolvent was prepared. A separate solution of 174 g. of thebeta-monoamine mixture in 87 g. of xylene solvent was prepared. Theepichlorohydrin solution was heated to a pot temperature of 105C. withstirring and one-half of the amine solution was added and the mixturestirred and heated to a pot temperature of 110C. Thereafter theremaining portion of the amine solution was added and the mixture wasstirred and heated to a maximum pot temperature of about 145C. for about7 hours. Then 48 g. of 50 percent sodium hydroxide solution was addedand the stirring and heating to a pot temperature starting at 145C. anddropping to 116C. over a period of about 3% hours. Here again, water wasadded, the phases separated and the reaction product shaken with 8 gramsof adsorbent silica gel and filtered. The reaction product was recoveredas a clear light brown liquid.

A portion of the above reaction product was subjected to vacuumdistillation to remove the xylene solvent and to leave the reactionproduct as an amber clear liquid having an average molecular weight of659, a total basic nitrogen equivalent weight of 2.76, a tertiary basicnitrogen equivalent weight of 1.69 and an acidity of 0.076 meq/g. Thereaction product had an average of 1.9 recurring units.

EXAMPLE v The reaction product of this example is prepared by reactingequal mole proportions of N-l-methylheptylamine with epichlorohydrin.The epichlorohydrin is formed as a solution in toluene solvent and theN-lmethylheptylamine is formed as a separate solution in toluenesolvent. The epichlorohydrin solution is stirred and heated to atemperature of 100C. and one-half portion of the N-l-methylheptylaminesolution is added thereto with stirring and heating to 100C. then theremaining N-l-methylheptylamine solution is added and the mixture isstirred and heated to 120C. An equal mole proportion of 25 percent byweight sodium hydroxide solution is added in increment portions withcontinued stirring and heating to a temperature of 125C. Followingcompletion of the reaction, the sodium chloride formed during thereaction is removed by filtering and the product is recovered as asolution in toluene solvent. Additional toluene solvent is added to forma final solution containing the active ingredient in a 50 percent byweight concentration.

EXAMPLE V1 The reaction product of this example is prepared by reactingone mole proportion of N-l-methyldecyl propylene-diamine with one moleproportion of epichlorohydrin. Here again, the epichlorohydrin and theamine are formed as separate solutions in xylene solvent. Theepichlorohydrin solution is stirred and heated to a temperature of C.and one-half of the amine solution is added thereto with stirring andcontinued heating at 80C., after which the remaining portion of theamine solution is added with stirring and heating to a temperature ofabout C. Following reaction of the epichlorohydrin and amine, an equalmole proportion of 35 percent by weight sodium hydroxide solution isadded and the mixture is stirred and heated at C. Following completionof the reaction, the reaction mixture is withdrawn and filtered hot toremove the sodium chloride formed during the reaction. The reactionproduct is recovered and subjected to vacuum distillation to remove thexylene solvent and to recover the reaction product as a clear liquid.

EXAMPLE VII Another reaction product is prepared in substantially thesame manner as described in Example VI except that the beta-diamine usedis a mixture of betadiamines marketed under the trade name of DuomeenL-ll. This mixture contains beta-diamines having from 14 to about 17carbon atoms per molecule. The reaction is effected by forming separatesolutions of epichlorohydrin in toluene solvent and the betadiamines intoluene solvent. The beta-diamines are added in increment portions tothe heated and stirred mixture of epichlorohydrin solution. Potassiumhydroxide is added to form potassium chloride and to release theavailable amines for further reaction to form a polymericreactionproduct. Following completion of the reaction, the reactionmixture is filtered to remove the potassium chloride and then issubjected to vacuum distillation to recover the reaction product as aclear liquid.

EXAMPLE V111 As hereinbefore set forth, an unexpected and importantadvantage of the reaction products of the present invention preparedfrom the beta-amines is the low pourpoint, as well as the low cloudpoint. The pour point and cloud point of the reaction products ofExamples I, II, and III, prepared as solutions containing 50 percent byweight of active ingredients, are reported in the following table. Forcomparative purposes, the pour point and cloud point of the reactionproduct prepared from epichlorohydrin and alpha-amine (hydrogenatedtallowamine) are also reported in the table. The reaction productprepared from the alphaamine was made in substantially the same manneras described in Examples I through III except that the amine was analpha-amine instead of a beta-amine.

TABLE I Reaction Product Pour Point Cloud Point Example I -1 F. l 10F.Example II -l 10F. -l10fF. Example III -l 10F. -l 10F. Prepared fromhydrogenated tallowamine +60F. +62F.

From the data in the above table, it will be seen that the reactionproducts prepared from the beta-amines had pour and cloud points of lessthan minus 110F. Accordingly, no problem of solidification will occurduring storage or use of these solutions of reaction products. Incontrast, the reaction product prepared from the alpha-amine(hydrogenated tallowamine) in 50 percent solution had pour points andcloud points of about 60F. and solidification problems are encounteredwhen the temperature of storage and/or'use is below this temperature.

EXAMPLE IX As hereinbefore set forth, the additives of the presentinvention are particularly applicable for use in fuel oil. These wereevaluated in various methods. In a one-day fuel stability test, 500 ml.of commercial No. 2 fuel oil are placed in a sealed bottle, into whichthree iron strips are also placed, and the system is purged with oxygenand sealed. The bottle then is heated at 212F. for 16 hours, after whichthe fuel oil is allowed to cool, filtered and the deposit formation isdetermined by weighing.

When evaluating in the above manner, a control or blank sample of thefuel oil, without additive, developed 15.4 mg. of deposit per 100 cc. offuel oil. The following table reports these data and the resultsobtained when other samples of the fuel oil containing the additive ofthe present invention were evaluated in the same manner. The additivesof the present invention comprised 50 percent weight solutions in xylenesolvent and were used in a concentration of 60 parts per million of thesolution (30 parts per million of active ingredients).

As hereinbefore set forth, the additives of the present inventionadvantageously are used in admixture with a copper deactivator. Thefollowing table also reports results of evaluations made with samples ofthe fuel oil containing 60 parts per million of the additive solution(30 parts per million of active ingredients) and 2 parts per million ofsalicylal diaminopropane copper deactivator.

TABLE n Deposit Formation Additive mg. of deposit per cc. of oil None15.4 60 ppm of Example l solution 60 ppm of Example ll solution 60 ppmof Example I]! solution From the data in the above table it will be seenthat the control sample, without additive, developed 15 .4 mg. ofdeposit per 100 cc. of fuel oil. In contrast, the samples containing 60parts per million of the additive solutions of the present inventionreduced these deposits to less than about 4 mg. per 100 cc. of fuel oil.

The table also shows the synergistic effect obtained by using theadditive solution in admixture with the copper deactivator. Thiscombination reduced the deposit formation to less than about 0.4 mg. ofdeposit per 100 cc. of oil.

For comparative purposes, a sample of the fuel oil containing 60 partsper million of a 50 percent by weight reaction product solution preparedin substantially the same manner but using alpha-amine (hydrogenatedtallowamine), when evaluated in the same manner, developed 4.8 mg. ofdeposit per 100 cc. of oil. Another sample containing 60 parts permillion of this reaction product and 2 parts per million of salicylaldiaminopropane developed 2.0 mg. of deposit per 100 cc. of oil. It willbe noted that in this case the combination of reaction product andcopper deactivator did not exhibit the high synergistic action wasexperienced in the case of the mixture of copper deactivator andreaction products prepared from betaamines.

EXAWLE X The additives of the present invention also were evaluated in a3-month fuel oil stability test in which samples of the fuel oil, withand without additives, were stored in pyrex Erlenmeyer flasks in thedark for 3 months at F., after which time the fuel oil was allowed tocool, then filtered and the deposit weighed. The fuel oil used in thisseries of tests was a commercial No. 2 fuel oil having a specificgravity of 0.8628 and a boiling range of from 399 to 628%. The resultsof these evaluations are reported in the following table.

TABLE III Deposit Formation 32 ppm of additive solution of Example ll0.2 32 ppm of additive solution of Example Ill 32 ppm of additivesolution of Example [V 0.5

Here again, it will be noted that the additive solutions of the presentinvention were very efiective in retarding deposit formation of the fueloil during storage.

EXAIVIPLE XI A 50 percent by weight solution in xylene solvent of thereaction product, prepared as described in Example I, is used as anadditive to prevent heat exchanger deposits in a gasoline reforming unitin which the gasoline is heated to a temperature of 890F. and passed,together with hydrogen, through a reaction chamber containing a bed ofcatalyst comprising alumina-platinum combined halogen. A series of threeheaters and reaction chambers are used. The reaction products from thelast reaction chamber are-passed in indirect heat exchange with thegasoline charge to the process. This serves to partially cool the hotreaction products and to partially heat the incoming gasoline charge.Difficulty is experienced because of deposit formation in the heatexchanger tubes. In order to minimize such deposit formation and toconsiderably extend the operatability of the heat exchanger, 8 parts permillion of the additive solution of Example I are incorporated in thehot reaction products leaving the reaction chamber prior to entering theheat exchanger.

I claim as my invention:

1. The reaction product formed by the reaction, at. a temperature offrom about 50 to about 200C, of (1) from 1 to 1.5 mole proportions of anepihaiohydrin compound selected from the group consisting ofepichlorohydrin, l,2-epoxy-4-chlorobutane, 2,3- epoxy-4-chlorobutane, l,2-epoxy-5-chloropentane, 2,3-epoxy-5-chloropentane and correspondingbromo and iodo compounds with (2) from 1 to 2 mole proportions of abeta-amine containing from about 4 to about 50 carbon atoms, saidbeta-amine having an alkyl group attached to a nitrogen atom at its betacarbon atom, thereafter reacting with an inorganic base selected fromthe group consisting of sodium hydroxide and potassium hydroxide at atemperature of from about 60 to about 200C. to liberate the free amineand to form an inorganic halide salt.

2. The reaction product of claim 1 being a polymeric reaction productformed by the reaction of epichlorohydn'n with the beta-amine, and saidpolymeric reaction product is formed by-further reacting at atemperature of from about to about 200C.

3. The reaction product of claim 2 being a polymeric reaction product inwhich the first reaction is at a temperature of from about 60 to about150C., said inorganic base is sodium hydroxide which is reacted at atemperature of from about 75 to about 150C. to liberate the free amine,and thereafter reacting at a temperature of from about to C. to form thepolymeric reaction product.

2. The reaction product of claim 1 being a polymeric reaction productformed by the reaction of epichlorohydrin with the beta-amine, and saidpolymeric reaction product is formed by further reacting at atemperature of from about 75* to about 200*C.
 3. The reaction product ofclaim 2 being a polymeric reaction product in which the first reactionis at a temperature of from about 60* to about 150*C., said inorganicbase is sodium hydroxide which is reacted at a temperature of from about75* to about 150*C. to liberate the free amine, and thereafter reactingat a temperature of from about 80* to 150*C. to form the polymericreaction product.